CN101842417A - Water-based dispersions of highly-branched polymers - Google Patents
Water-based dispersions of highly-branched polymers Download PDFInfo
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- CN101842417A CN101842417A CN200880108931A CN200880108931A CN101842417A CN 101842417 A CN101842417 A CN 101842417A CN 200880108931 A CN200880108931 A CN 200880108931A CN 200880108931 A CN200880108931 A CN 200880108931A CN 101842417 A CN101842417 A CN 101842417A
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- branched polymers
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- 229920000642 polymer Polymers 0.000 title claims abstract description 53
- 239000006185 dispersion Substances 0.000 title claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 19
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000011347 resin Substances 0.000 claims description 119
- 229920005989 resin Polymers 0.000 claims description 119
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 239000002253 acid Substances 0.000 claims description 40
- 239000004593 Epoxy Substances 0.000 claims description 39
- 239000000126 substance Substances 0.000 claims description 28
- 239000004925 Acrylic resin Substances 0.000 claims description 27
- 229920000178 Acrylic resin Polymers 0.000 claims description 27
- -1 poly(propylene oxide) Polymers 0.000 claims description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 19
- 150000002148 esters Chemical class 0.000 claims description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 16
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 13
- YARNEMCKJLFQHG-UHFFFAOYSA-N prop-1-ene;styrene Chemical compound CC=C.C=CC1=CC=CC=C1 YARNEMCKJLFQHG-UHFFFAOYSA-N 0.000 claims description 12
- 150000002118 epoxides Chemical group 0.000 claims description 10
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 8
- 238000001879 gelation Methods 0.000 claims description 7
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- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 6
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims description 5
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 5
- UBLAMKHIFZBBSS-UHFFFAOYSA-N 3-Methylbutyl pentanoate Chemical compound CCCCC(=O)OCCC(C)C UBLAMKHIFZBBSS-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 4
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- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims description 3
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 claims description 3
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 3
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 3
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 claims description 3
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 claims description 3
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 2
- LMAUULKNZLEMGN-UHFFFAOYSA-N 1-ethyl-3,5-dimethylbenzene Chemical compound CCC1=CC(C)=CC(C)=C1 LMAUULKNZLEMGN-UHFFFAOYSA-N 0.000 claims description 2
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 claims description 2
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-UHFFFAOYSA-N 0.000 claims description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 2
- ZVYGIPWYVVJFRW-UHFFFAOYSA-N 3-methylbutyl prop-2-enoate Chemical compound CC(C)CCOC(=O)C=C ZVYGIPWYVVJFRW-UHFFFAOYSA-N 0.000 claims description 2
- 241001448862 Croton Species 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 claims description 2
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 claims description 2
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 claims description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000113 methacrylic resin Substances 0.000 claims 8
- 238000000576 coating method Methods 0.000 abstract description 31
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- 229910021641 deionized water Inorganic materials 0.000 description 14
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 5
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- LSWYGACWGAICNM-UHFFFAOYSA-N 2-(prop-2-enoxymethyl)oxirane Chemical compound C=CCOCC1CO1 LSWYGACWGAICNM-UHFFFAOYSA-N 0.000 description 3
- 102100026735 Coagulation factor VIII Human genes 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
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- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
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- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical compound C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 2
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 description 2
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
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- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
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- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
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- YHCCCMIWRBJYHG-UHFFFAOYSA-N 3-(2-ethylhexoxymethyl)heptane Chemical compound CCCCC(CC)COCC(CC)CCCC YHCCCMIWRBJYHG-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DTGKSKDOIYIVQL-MRTMQBJTSA-N Isoborneol Natural products C1C[C@@]2(C)[C@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-MRTMQBJTSA-N 0.000 description 1
- 229920005692 JONCRYL® Polymers 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
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- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
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- RUZYUOTYCVRMRZ-UHFFFAOYSA-N doxazosin Chemical compound C1OC2=CC=CC=C2OC1C(=O)N(CC1)CCN1C1=NC(N)=C(C=C(C(OC)=C2)OC)C2=N1 RUZYUOTYCVRMRZ-UHFFFAOYSA-N 0.000 description 1
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- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/182—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents
- C08G59/186—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents with acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/34—Epoxy compounds containing three or more epoxy groups obtained by epoxidation of an unsaturated polymer
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D135/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D135/06—Copolymers with vinyl aromatic monomers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
Abstract
The present invention provides aqueous dispersions of highly-branched polymers for coating applications and methods for making the polymers. The polymers may have high molecular weights and desirably take the form of microgels. The polymers and dispersions may be formulated with functionalities, viscosities, and solids contents that make them well-suited for use in a variety of coatings including, but not limited to, 2-pack coatings, ultraviolet (UV) curable coatings, inks, and air-dry coatings.
Description
The cross reference of related application
This U.S. patent application case requires the right of priority of the U.S. Provisional Patent Application 60/952,689 submitted on July 30th, 2007, for all purposes, the full content of this patent is incorporated herein by reference.
Technical field
In general, the present invention relates to the aqueous based dispersions of highly-branched polymers and the preparation method of this dispersion.
Background of invention
High-molecular weight highly-branched polymers (comprising microgel (microgel)) can be used in many coating.As at United States Patent (USP) 6,034, to be put down in writing in 157, these polymkeric substance can prepare by making the reaction of sour functionality acrylic resin and di-epoxy compounds.But polymerization and dispersion because take place, so be not suitable for low voc coatings in many branched polymers in organic solvent.In addition, no matter be aqueous-based polymers or solvent based polyalcohol, the acid number of these polymkeric substance all may limit the solid content by the coating composition of these polymer manufacture.
Summary of the invention
In general, the present invention relates to prepare the method for highly-branched polymers, it is that resin (arylic oratyrene-arylic resin) reacts with the many epoxy functional resin with at least two epoxide groups and prepares first highly-branched polymers that this method comprises the following steps: to make the sour functionality acrylic resin that is scattered in the water or styrene-propene acid; And, make the reaction of described first highly-branched polymers and monocycle oxygen functionality resin or compound to form the aqueous dispersion of second highly-branched polymers and/or further functionalized polymkeric substance subsequently.
The aqueous dispersion of second highly-branched polymers is highly suitable for various coating, comprises printing ink, two component (2-pack) epoxy coating, UV-light (UV) is coating material solidified and air drying type coating (air dry coating).Aqueous dispersion also can be used as the binding agent and the middle chromatography varnish (overprint varnish) that uses of plane plastic arts (graphic arts) of printing-ink.
Detailed Description Of The Invention
The method that the invention provides the aqueous dispersion of the highly-branched polymers that is used for coating and prepare this polymkeric substance.This polymkeric substance can have high molecular, and can desirably adopt the microgel form.Polymkeric substance and formulated can be become have to make the form of its functional group that is highly suitable for various coating, viscosity and solid content, described coating is including, but not limited to two component epoxy coating, UV-light or peroxide cure coating and air drying type coating.This polymkeric substance and dispersion also can be used as the chromatography varnish that uses in binding agent in the printing-ink and the plane plastic arts.
A kind of basic skills that forms described polymkeric substance comprises the steps: to make the sour functionality acrylic resin (arylic resin) that is scattered in the water and contains many epoxy functional resin reaction of at least two epoxy-functionals to prepare first highly-branched polymers.What expect is that this aqueous dispersion medium does not contain or do not contain substantially organic solvent.Acrylic resin has higher acid number, and this can realize that good dispersion is to form first highly-branched polymers.Increase the degree of branching and the molecular weight of polymkeric substance with the reaction of many epoxy functional resin, caused having formed microgel in some cases.This reactions steps has determined the viscosity of polymkeric substance, and at the situation of the microgel particle diameter of having made decision.This first polymkeric substance and monocycle oxygen functionality resin or compound are reacted to form the aqueous dispersion of second highly-branched polymers or microgel.This second reaction has further consumed the number acid functional group on first polymkeric substance, thereby has reduced acid number, and can realize that solid content is higher than the dispersion of other modes.In addition, this second reaction is also further carried out functionalized to polymkeric substance.The polymkeric substance of gained has excellent waterproofness (water-resistance) and toughness, film forming under low VOC content, and have high glossiness (glosspotential).
Term as used herein " microgel " is meant dispersion of polymer particles, these polymer beads are inner take place crosslinkedly but in external phase crosslinked without any obvious amount, thereby given lower viscosity of dispersion and higher solid content.These microgels have formed the successive network when film forming.
These reactions are important according to said sequence, this be because if sour functionality resin at first with the reaction of monocycle oxygen functionality resin or compound, caused acid number reduces and the pH rising meeting followed causes viscosity sharply to increase owing to the uncoiling of polymkeric substance.This viscosity increase can make these dispersions not be suitable for coating.On the contrary, make sour functionality resin at first with many epoxy functional resin reaction, produced not can uncoiling highly-branched polymers, rolling up of viscosity can not be taken place therefore subsequently with monocycle oxygen functionality resin or compound reaction the time.This will explanation in following embodiment 1.
The water dispersible that uses among the present invention acid functionality acrylic resin desirably is the carboxylic-acid functional resin, and described carboxylic-acid functional resin is prepared by one or more acrylic or methacrylic acid mono and one or more other ethylenically unsaturated monomers polymerizations.These other monomers can comprise the styrenic (styrenics) or their combination of the esters of acrylic acid of no functionality or methyl acrylic ester, no functionality.Also hydroxyl functional monomer and other functional monomer (for example diacetone-acryloamide(DAA) (DAAM) and methacrylic acid acetoacetyl 2-ethoxyethyl acetate (AAEMA)) polymerization can be gone in the acrylic resin.If polymkeric substance is used as dual-component coating, it is favourable then comprising hydroxy functional group in acrylic resin.DAAM and AAEMA provide at room temperature crosslinked dispersion can take place.
The acrylic resin of acid functionality has lower molecular weight, higher acid number and the possible hydroxyl value of certain limit usually.For example, the number-average molecular weight (M of acrylic resin
n) can be about 1000～10000, acid number can be about 25～300, and/or hydroxyl value (being hydroxyl equivalent) can be about 1～250.But also can use the sour functionality acrylic resin of character outside these scopes, condition be they be water dispersible and can form branched polymer with Resins, epoxy reaction.
Acid functionality resin can be by known method preparation.For example, this resin can be the emulsion resin (emulsion resin) that forms when chain transfer agents exists, and maybe can prepare with successive high temperature polymerization method.At United States Patent (USP) 4,414, put down in writing the appropriate method that forms sour functionality resin in 370,4,529,787,4,546,160,6,552,144,6,194,510 and 6,034,157, whole disclosures of these patents are incorporated herein by reference.
Can provide the example of the hydroxyl functional acrylic monomer of sour functionality resin to comprise esters of acrylic acid and methyl acrylic ester through polymerization.These monomeric examples contain the monomer of one or more hydroxyls including, but not limited to those, for example: vinylformic acid 2-hydroxyl ethyl ester, methacrylic acid 2-hydroxyl ethyl ester, vinylformic acid 2,3-hydroxypropyl acrylate, methacrylic acid 2,3-hydroxypropyl acrylate, vinylformic acid 2,4-hydroxy butyl ester and methacrylic acid 2,4-hydroxy butyl ester, or the mixture of these esters of acrylic acids or methyl acrylic ester.
Can provide the no functionality esters of acrylic acid of sour functionality resin and the monomeric example of methyl acrylic ester including, but not limited to methyl acrylate through polymerization, ethyl propenoate, the vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, the vinylformic acid n-pentyl ester, the vinylformic acid isopentyl ester, vinylformic acid iso-borneol (isobornyl) ester, the just own ester of vinylformic acid, vinylformic acid 2-ethyl butyl ester, 2-EHA, the vinylformic acid n-octyl, vinylformic acid ester in the positive last of the ten Heavenly stems, vinylformic acid methyl cyclohexane ester, vinylformic acid ring pentyl ester, cyclohexyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, methacrylic acid 2-hydroxyl ethyl ester, n propyl methacrylate, n-BMA, isopropyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, the methacrylic acid n-pentyl ester, the just own ester of methacrylic acid, the methacrylic isoamyl valerate, the secondary butyl ester of methacrylic acid, the methacrylic tert-butyl acrylate, methacrylic acid 2-ethyl butyl ester, methyl methacrylate base cyclohexyl, the methacrylic acid cinnamic ester, methacrylic acid crotons ester, cyclohexyl methacrylate, methacrylic acid ring pentyl ester, methacrylic acid 2-ethoxy ethyl ester and isobornyl methacrylate.Preferred no functionality acrylic acid series and no functionality metha crylic monomer are: butyl acrylate, butyl methacrylate, methyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate and their combination.Also can use two or more aforesaid propylene esters of gallic acid and the monomeric mixture of methyl acrylic ester arbitrarily.
Polymer product of the present invention also can randomly comprise one or more no functionality styrene monomers.Be used for styrene monomer of the present invention including, but not limited to the mixture of vinylbenzene, alpha-methyl styrene, p-methylstyrene, t-butyl styrene, chloro styrene and these kinds.The preferred styrene monomer that is used for the inventive method comprises vinylbenzene and alpha-methyl styrene.In the methods of the invention, the many epoxy functional resin with two or more epoxy-functionals can be diepoxy resin (diepoxy resin) or many epoxy functional resin.United States Patent (USP) 6,194,510 have put down in writing the polycondensate of epoxy functional, and it can be used as many epoxy functional resin of the present invention.The oxirane value of many epoxy functional resin (being epoxy equivalent (weight)) can be about 100～1000 (for example about 100～500 or about 100～350), but the resin of character outside these scopes also is operable.In some embodiments, many epoxy functional resin comprises the 2-glycidyl ether resin.For example, many epoxy functional resin can comprise cyclohexanedimethanodiglycidyl diglycidyl ether, poly(propylene oxide) diglycidylether or bisphenol A diglycidyl ether.
Can use known method, comprise those at United States Patent (USP) 6,194, the method for record makes many epoxy functional resin and sour functionality resin reaction in 510 and 6,034,157.These methods generally include following steps: with the aqueous dispersion of the sour functionality resin reaction chamber of packing into, in reaction chamber, add many epoxy functional resin, reactant is reacted to each other being enough to form under the temperature and time condition of highly-branched polymers or microgel.Embodiment part hereinafter exemplifies and has illustrated these methods in further detail.According to the polymer property of final expectation, the variation range of the sour functionality resin in the reaction and the mol ratio of many epoxy functional resin can be very wide.
Naturally, highly-branched polymers as the reaction product of sour functionality resin and many epoxy functional resin, is compared with its sour functionality resin of preparation, has higher molecular weight, lower acid number and the hydroxyl value of Geng Gao.For example, the M of this polymkeric substance
nCan be from about 2200 to up to gelation point, even surpass gelation point, and have about 20～275 acid number.Depend on whether sour functionality acrylic resin has hydroxy functional group, and the highly-branched polymers of gained can have about 10～260 hydroxyl value.But also can prepare the highly-branched polymers of character outside these scopes.
The monocycle oxygen functionality resin that forms end product with the highly-branched polymers reaction can be (wherein epoxide group is the unique functional group on resin or the compound) of simple function, it maybe can be multi-functional (wherein resin or compound comprise at least a other functional group, for example hydroxyl).In some embodiments, monocycle oxygen functionality resin or compound can be glycidyl ether or glycidyl ester.Suitable monocycle oxygen functionality resin or the specific examples of compound are including, but not limited to the glycidyl ester of glycidyl methacrylate, neodecanoic acid, the monoglycidyl ether of dihydroxyphenyl propane, glycidyl allyl ether and 2-ethylhexyl glycidyl ether.Glycidyl methacrylate is particularly useful in the formation of ultraviolet-curing paint.Hydrophobic monocycle oxygen functionality compound, for example those are particularly suitable for preparing air drying type coating derived from the compound of many unsaturated alkyls or aralkyl.The polymer property that depends on final expectation, the variation range of the mol ratio of highly-branched polymers in the reaction and monocycle oxygen functionality resin can be very wide.
Final high-molecular weight highly-branched polymers is usually expressed as the form of microgel, and compares with its highly-branched polymers of preparation, has higher molecular weight, lower acid number and the hydroxyl value of Geng Gao.For example, the M of this polymkeric substance
nCan be from about 2500 to up to gelation point, even surpass gelation point, and have about 15～250 acid number and about 10～260 hydroxyl value.But also can prepare the end product of character outside these scopes.The aqueous dispersion of polymkeric substance is applicable to multiple coating.Because polymer dispersed is in water, so do not need high-load VOC, it is enough low that viscosity just can keep.In addition, with by by sour functionality acrylic resin and epoxy functional resin reaction with two or more functional groups, but omit the similar polymkeric substance institute coatings formulated for preparing with the end reaction of monocycle oxygen functionality resin or compound and compare, the end product that acid number reduces has been realized the higher coating of preparation solid content.For example, in some embodiments, can prepare the aqueous dispersion that solid content is at least the high molecular highly-branched polymers of 35 weight %.This comprises that solid content is at least the dispersion of about 38 weight %, comprises that also solid content is at least about the dispersion of 40 weight %.Therefore, than other known microgels, microgel of the present invention provides the coating of better low VOC, high solids content.
Abbreviation used herein is:
AA is the abbreviation of " vinylformic acid ";
AAEMA is the abbreviation of " methacrylic acid acetoacetyl 2-ethoxyethyl acetate ";
AGE is the abbreviation of " glycidyl allyl ether ";
ARx is the abbreviation of " sour functionality resin ", and wherein x is the serial number that is used for identifying sour functionality resin various preparations or that use;
AV is the abbreviation of " acid number ";
BA is the abbreviation of " butyl acrylate ";
BCM is the abbreviation of " 1,000,000,000 cus are analox per square inch ";
Blist is the abbreviation of " bubbling (blister) ";
Brk is the abbreviation of " destroying (break) (slightly penetrating (slight break through)) ";
CHDMDG is the abbreviation of " cyclohexyl dimethanol diglycidylether ";
CTA is the abbreviation of " chain transfer agents ";
CTER is the abbreviation of " chain transfer emulsion resin ";
DAAM is the abbreviation of " diacetone-acryloamide(DAA) ";
DER is the abbreviation of " diepoxy functionality resin ";
DN is the abbreviation of " degree of neutralization ";
DIW is the abbreviation of " deionized water ";
EHA is the abbreviation of " 2-ethylhexyl acrylate ";
HBNP is the abbreviation of " hyperbranched nano particle ";
HDI is the abbreviation of " 1, the 6-hexamethylene diisocyanate ";
HDPE is the abbreviation of " high density polyethylene(HDPE) ";
HEMA is the abbreviation of " methacrylic acid 2-hydroxyl ethyl ester ";
IPDI is the abbreviation of " isophorone diisocyanate ";
LDPE is the abbreviation of " new LDPE (film grade) ";
MAA is the abbreviation of " methacrylic acid ";
MEK is the abbreviation of " methylethylketone ";
MER is the abbreviation of " monocycle oxygen functionality resin ";
MMA is the abbreviation of " methyl methacrylate ";
M
nBe meant " number-average molecular weight ";
NE is the abbreviation of " not having effect ";
OH# is the abbreviation of " hydroxyl value ";
OPP is the abbreviation of " oriented polypropylene (oriented polypropylene) ";
Rng is the abbreviation of " ring ";
Sl is the abbreviation of " slightly ";
Sl stn is the abbreviation of " light contamination ";
STY is the abbreviation of " vinylbenzene ";
T
gIt is the abbreviation of " second-order transition temperature ";
Th is the abbreviation of " passing ";
UV is the abbreviation of " UV-light "; And
VOC is the abbreviation of " volatile organic matter ";
When being used for this paper, " pact " can be understood by those skilled in the art, and according to its applied context some degree change will be arranged.If according to the applied context of term, when those of ordinary skills did not know it with justice, what " pact " represented this concrete term reached positive and negative 10% most.When " pact " when being used to modify scope, it is applied to modifying entire area, and is not only first value of this scope.For example, unless specify in addition, can should be understood to from about X to about Y to the scope of Y beginning from about X.
The invention that this paper illustrative is described can suitably be implemented under the not concrete disclosed any key element of this paper or multiple key element, restriction or the non-existent situation of multiple restriction.Therefore, for example should broadly and not have that any restriction understands that term " comprises ", " comprising ", " containing " etc.In addition; term used herein and statement are descriptive term rather than restrictive terms; and shown in the use of these terms and statement is not intended to get rid of or any Equivalent of described feature or its part, but think that various modifications may be within the scope of protection of present invention.In addition, phrase " substantially by ... form " be understood as that and comprise that those concrete key elements of quoting and those can not produce other key element of substantial effect to the claimed basic and new feature of the present invention.Phrase " by ... form " got rid of any key element that does not specify.
Those skilled in the art can easily recognize, for all purposes, the scope discussed to some extent can and really its all subrange have been described necessarily, and this all class subranges has also constituted part and parcel of the present invention.All scopes of listing can easily be regarded as, and same scope is described as fully or makes this scope be subdivided at least two five equilibriums, trisection, the quartern, five five equilibriums, ten five equilibriums that equate, etc.As non-limiting instance, each scope discussed in this article all can directly be subdivided into lower limit 1/3rd, middle(-)third and the upper limit 1/3rd, etc.
To in this specification sheets, quote all publications, patent application, granted patent and alternative document and be incorporated herein by reference, incorporate this paper in full into as a reference with it particularly and individually as the public publication that each is independent, patent application, granted patent or alternative document.As get rid of itself and herein the conflicting scope of definition with reference to the definition that comprises in the article of introducing.
To further specify the present invention with reference to the following example, these embodiment only are intended to explanation rather than intention limits the scope of the invention.Except as otherwise noted, all umbers all by weight.
Embodiment
Embodiment 1: the preparation of microgel aqueous dispersion
This embodiment illustrated sour functionality resin with monocycle oxygen functionality compound reaction before earlier with the importance of many epoxy functional resin reaction.In this research, acid functionality resin is called as " ARx " herein, wherein x is the serial number that is used for identifying various sour functionality resins, listed the preparation of various sour functionality resins in table 1, following reaction takes place in they and epoxy functional reactant: (1) AR1 only with the monocycle oxygen functionality resin reaction of glycidyl allyl ether (AGE); (2) AR1 only with many epoxy functional resin reaction of cyclohexyl dimethanol diglycidylether (CHDMDG); (3) AR1 reacts with AGE earlier, its product and CHDMDG reaction subsequently; And (4) AR1 reacts its product and AGE reaction then earlier with CHDMDA.
Except the monomer content of sour functionality acrylic resin, table 1 has also been listed its acid number (AV), M
n, second-order transition temperature (T
g), O
2Percentage is the preparation method when." SGO " be meant at United States Patent (USP) 6,552, the high temperature polymerization method of record in 144, and " emulsion " is meant the chain transfer emulsion process.
Table 1
| Resin | ??MMA | ??EHA | ??HEMA | ??BA | ??CTA | ??STY | ??AA | ??MAA | ??AV | ??M n | ??T g | ??O2％ | The preparation method |
| ??AR1 | ??49 | ??- | ??- | ??14 | ??- | ??27 | ??10 | ??- | ??77 | ??5126 | ??78 | ??23.5 | ??SGO |
| ??AR2 | ??16 | ??- | ??- | ??22 | ??- | ??44 | ??10 | ??8 | ??130 | ??5025 | ??75 | ??18 | ??SGO |
| ??AR3 | ??40 | ??18.3 | ??5 | ??- | ??1.7 | ??25 | ??- | ??10 | ??65 | ??6000 | ??45 | ??21.8 | Emulsion |
Table 2 has been listed the ratio of the reaction of each experiment, and the molecular weight of products therefrom, acid number (AV), solid content, pH and viscosity.DER is the abbreviation of diepoxy functionality resin, and MER is the abbreviation of monocycle oxygen functionality resin.
Table 2
| ??AR | ??DER | ??MER | ??Mn | ??Mw | ??Mz | ??AV | Solid weight % | ??pH | Viscosity (cP) |
| ??AR1 | ??- | ??- | ??5251 | ??16280 | ??29070 | ??75 | ??40 | ??7.27 | ??618 |
| ??AR1 | ??- | ??AGE | ??5410 | ??17890 | ??34759 | ??39 | ??39.7 | ??7.89 | High |
| ??AR1 | ??CHDMDA | ??- | ??6096 | ??65673 | ??252831 | ??62 | ??39.93 | ??7.45 | ??356 |
| ??AR1 | CHDMDA (back) | AGE (elder generation) | ??6125 | ??70068 | ??292592 | ??45 | ??39.75 | ??7.86 | ??18960 |
| ??AR1 | CHDMDA (elder generation) | AGE (back) | ??5613 | ??90153 | ??385359 | ??33 | ??40 | ??7.96 | ??353 |
As shown in table 2, when sour functionality resin elder generation and monocycle oxygen functionality resin reaction, dispersions obtained viscosity sharply raises.On the contrary, when sour functionality resin during, do not observe the rising of viscosity earlier with many epoxy functional resin reaction and then with monocycle oxygen functionality resin reaction.
Embodiment 2: the formation method of microgel
This embodiment has illustrated from the method for various sour functionality resins, many epoxy functional resin and monocycle oxygen functionality resins microgel.The preparation of various sour functionality resins (AR1-AR3) and acid number thereof, M in above-mentioned table 1, have been shown
n, T
g, O
2Per-cent and preparation method.
In shown here first three experiment, highly branched microgel prepares as follows.Sour functionality resin (is contained small amount of N H at deionized water
4OH) in the aqueous dispersion in (28% the solution) reaction chamber of packing into, and be heated to 85 ℃.In the 4th experiment, resin (AR3) is packed in the reaction chamber, and be heated to 85 ℃, add ammoniacal liquor down at 50 ℃ then.Then diepoxy functionality resin is added in the reaction chamber, and reaction was carried out 60 minutes.Again monocycle oxygen functionality resin is added in the mixture with first part of DIW, and make to be reflected at and carried out under 87 ℃ 180 minutes.Reaction mixture adds second part of DIW simultaneously in mixture then.
Used diepoxy functionality resin is cyclohexanedimethanodiglycidyl diglycidyl ether (epoxy equivalent (weight) is 160) (ERISYS GE-22 or Heloxy 107), poly(propylene oxide) diglycidylether (epoxy equivalent (weight) is 312) (ERISYS GE-24) and bisphenol A diglycidyl ether (epoxy equivalent (weight) is 178) (Epon 825) in this experiment.Used monocycle oxygen functionality resin is glycidyl ether (epoxy equivalent (weight) is 250) (Cardura E or ERISYS GS-110), the C of neodecanoic acid
12-C
14Alkyl glycidyl ether (epoxy equivalent (weight) is 287) (Heloxy 8) and 2-ethylhexyl ether (epoxy equivalent (weight) is 220) (ERISYS GE-6).
Table 3 has shown resin, DIW and the NH in every kind of starting acid functionality resin aqueous dispersion in each experiment
4The consumption of OH solution.Table 4 has shown the consumption of the sour functionality resin dispersion (AR), DER, MER and the DIW that are used to form every kind of microgel, and the DN of microgel and dispersion, acid number, T
g, OH#, solid content (weight %), pH and viscosity.The mol ratio of sour functionality resin/diepoxy functionality resin/monocycle oxygen functionality resin is respectively in four experiments: (1) 3/2.5/6; (2) 3/2.5/7; (3) 3/2.5/14; (4) 3/2.5/6.7.
Table 3
| ??(1) | ??(2) | ??(3) | ??(4) | |
| ??AR | ??40.6 | ??40.6 | ??40.4 | ??- |
| Deionized water | ??58.2 | ??58.2 | ??57.8 | ??- |
| ??NH 4OH(28％) | ??1.2 | ??1.2 | ??1.8 | ??- |
Table 4
| ??DER | ??MER | ??DIW??(1) | ??DIW??(2) | ??DN | ??AV | ??T g??(℃) | ??AR | ??OH??# | Solid weight % | ??pH | ??η??(cP) | |
| ??3.34 | ??3.69 | ??5 | ??5.35 | ??76 | ??28 | ??37 | ??(1) | ??82.62 | ??33 | ??39.5 | ??7.2 | ??218 |
| ??DER | ??MER | ??DIW??(1) | ??DIW??(2) | ??DN | ??AV | ??T g??(℃) | ??AR | ??OH??# | Solid weight % | ??pH | ??η??(cP) | |
| ??1.79 | ??3.91 | ??5 | ??3.52 | ??76 | ??28 | ??52 | ??(2) | ??85.78 | ??38 | ??38.7 | ??7.3 | ??135 |
| ??1.87 | ??6.47 | ??5 | ??7.5 | ??83 | ??39 | ??41 | ??(3) | ??79.6 | ??49 | ??39.9 | ??8.4 | ??33 |
| ??1.54 | ??3.71 | ??5 | ??7.52 | ??68 | ??25 | ??- | ??(4) | ??81.75 | ??51 | ??38.7 | ??8.1 | ??38 |
Embodiment 3: latex modified is become dissaving structure
Latex (the latex) (sample 100 of in three neck round-bottomed flasks, packing into, 400 grams), this latex is by 20% vinylbenzene, 35% 2-EHA, 33.3% butyl methacrylate, 1.67% the different monooctyl ester of thiohydracrylic acid and 10% methacrylic acid preparation.Use 14% NH
4OH solution (4.34 gram) neutralizes this latex.To be heated to 85 ℃ through the neutral emulsion then, and add diepoxide through 30 minutes (Heloxy 107,5.45 grams).After adding diepoxide, solution was kept 30 minutes down at 85 ℃, added simple function epoxide (Heloxy 8,11.48 grams) then through 30 minutes.Then temperature is increased to 87 ℃ and keep 150 minutes with the preparation modification latex.Cool off the latex (sample 102) of this modification then and filter, obtain the material with following character: 39.5% solid content, pH are 7.95, viscosity is 6cps (using #2 rotor (spindle) to measure under 50rpm).
Embodiment 4: latex modified is become dissaving structure
The latex (sample 101,400 gram) of packing in three neck round-bottomed flasks, this latex is by 20% vinylbenzene, 35% butyl acrylate, 10% methacrylic acid and 1.93% the different monooctyl ester preparation of thiohydracrylic acid.Use 14% NH
4OH solution (4.39 gram) neutralizes this latex.To be heated to 85 ℃ through neutral latex then, and add diepoxide through 30 minutes (Erisys GE-24,5.74 grams).After the adding diepoxide is finished, latex was kept under 85 ℃ 30 minutes, adding the simple function epoxide then through 30 minutes is glycidyl methacrylate (7.57 gram).Then temperature is increased to 87 ℃ and keep 150 minutes with the preparation modification latex.Cool off the latex (sample 103) of this modification then and filter, obtain the material with following character: 39.5% solid content, pH are 7.95, viscosity is 6cps (using the #2 rotor to measure under 50rpm).
Embodiment 5: with the prepared printing ink of the latex with dissaving structure
Prepare printing ink with every kind of polymkeric substance and Flexiverse BFD1121, wherein Flexiverse BFD1121 is the phthalocyanine blue pigment dispersion of buying from Sun Chemical.Prepare printing ink in 150 milliliters the plastic cup on Speedmixer.At first dispersion is added in the cup, add polymkeric substance and deionized water then.Then printing ink was mixed 30 seconds under 2400rpm.The viscosity of four kinds of experiment printing ink by this method preparation when not adding any water all less than 27 seconds (in Signature Zahn#2cup, measuring).
Use pond volume (cell volume) as the manual proof press of 360-line (handproofer) of 2.3BCM with respect to standard ink base (ink base) (Joncryl 2646) (hand-proof) the every kind of printing ink of manually drawing a design abreast.Printing ink is drawn a design on four kinds of different plastic-substrates, and these four kinds of plastic-substrates are: the HDPE-42Dyne that Corona handles; The LDPE-42Dyne that Corona handles; The OPP-44Dyne of Acrylic coating; And Corona handles poly(lactic acid) (the Ecoflex)-43Dyne of modification.
After drawing a design, with the manual dry print of hair dryer 2 seconds.After the drying, the print placement is spent the night.Use 3M 610 adhesive tapes to measure adhesive tape clinging power (tape adhesion).Also measure colour density (colordensity) and with standard relatively.
Table 5
| Preparation | ??A | ??B | ??C | ??D | ??E |
| Standard | ??50.0 | ||||
| ??100 | ??60.0 | ||||
| ??101 | ??60.0 | ||||
| ??102 | ??60.0 | ||||
| ??103 | ??60.0 | ||||
| ??Flexiverse?BFD | ??40.0 | ??40.0 | ??40.0 | ??40.0 | ??40.0 |
| ??1121 | |||||
| Deionized water | ??10.0 | ??0.0 | ??0.0 | ??0.0 | ??0.0 |
| Total amount | ??100.0 | ??100.0 | ??100.0 | ??100.0 | ??100.0 |
| Viscosity (second, Zahn#2) | ??22.5 | ??224 | ??20.6 | ??20.0 | ??19.7 |
Table 6: printing ink result data:
| Standard | Preparation 100 | Preparation 101 | Preparation 102 | Preparation 103 | |
| % clinging power HDPE | ??100 | ??100 | ??100 | ??100 | ??100 |
| % clinging power LDPE | ??100 | ??100 | ??100 | ??100 | ??100 |
| % clinging power OPP | ??95 | ??70 | ??90 | ??75 | ??90 |
| % clinging power Ecoflex | ??75 | ??60 | ??75 | ??60 | ??75 |
| With respect to transfer (difference on colour density) in standard on the OPP | Standard | ??-20.5％ | ??-12.3％ | ??-11.8％ | ??-9.4％ |
Embodiment 6: the water base pair of component that uses hyperbranched polymer
Used HBNP is by following prepared in reaction: contain carboxylic acid functional and hydroxy functional group low-molecular-weight acrylic acid polymer and diepoxy functionality resin reaction, react with the simple function epoxy modifying agent again.All being reflected in the water finished, and do not use solvent or other catalyzer.Acid functional group on epoxy-functional and the acrylic acid series reacts at 85-90 ℃ in an advantageous manner.Acrylic acid polymer in this experiment uses the preparation of chain transfer emulsion process.
The M of used low molecular weight acrylic acid series polymeric compounds
nBe about 6000, acid number is 65.This has produced the average functionality of about 7 carboxyls of each molecule.This acrylic acid polymer is and the epoxide reactive multi-functional acid of two functionalities.When the mol ratio of acrylic acid series and epoxide when changing for 3: 1～1: 1, the molecular weight of polycondensate is increased to gelation point and surpasses gelation point.Add the simple function epoxy resin to reduce acid number and to increase hydroxy functional group.Acrylic acid polymer (M
nBe 6000) and diepoxide (di-epoxy) (M
nBe 320) between an advantage of difference in size be: do not need to use a large amount of (based on weight percent) epoxide just can realize the change of molecular weight.Another advantage is: owing to finishing in the disperse phase that is reflected at colloidal solid, so viscosity can not raise.
To the hydroxyl value of this acrylic acid polymer, the type and the T of soft monomer
gCharacterize.Mol ratio is used for characterizing hyperbranched degree.HDI is used for characterizing the distribution of water base isocyanic ester than IPDI, mol ratio.Hyperbranched polymers is placed the beaker whipping appts, and add suitable isocyanic ester and water together, so that the final solid content of mixture is 40%.On the Leneta testing plate, carry out blade coating (Drawdown), and after finishing, per hour carry out blade coating once more, or carry out blade coating always until gel formation.In preparation back 1 hour, also prepare an aluminum slice and stick into capable Konig and MEK tolerance (resistance) test.And test is in the chemical resistant properties of the Leneta testing plate (chart) of 1 hour and 3 hours.And measure the gloss value of all testing plate.
Be displayed in Table 7 used CTER.T
gFollow hydroxyl value to change.T
gCalculated value and T
gThe BA that relatively demonstrates of observed value is harder monomer, and obviously is stiffer than calculated value.
Every kind of acrylic resin all is used for by reacting and the HBNP of preparation standard with Heloxy 107 (H 107) and Heloxy 8 (H8).Heloxy 107 is diglycidylethers of cyclohexanedimethanol, and Heloxy8 is C
12-C
14The monoglycidyl ether of alcohol.Every kind of polymkeric substance all be to use 3 moles CTER and 2.5 moles H 107, re-use 7 moles H8 prepared.Two kinds of HBNP polymkeric substance in addition are from sample 1 preparation, change only to be H107 is adjusted into 2 moles and 3 moles, H8 is adjusted into 8 moles and 6 moles simultaneously, and are identical with the amount of maintenance ester.All data in table 8, have been listed.The hydroxy radical content of final HBNP is the hydroxyl sum of the epoxy addition reaction of the hydroxy radical content of CTER and adding.The epoxy addition most probable produces secondary hydroxyl, so its reactivity may be not as being used for the HEMA of CTER.Also interesting is, the particle diameter of HBNP and initial CTER particle diameter difference are little, this show this reaction be likely occur in intragranular.
In standard testing, various HBNP and HW-180 are at NCO: the OH ratio is to react under 1: 1 the condition.Also at NCO: the OH ratio is two kinds of HBNP with different mol ratio of test under 1.5: 1 the condition.In the reaction of IPDI type, study BA: the difference of EHA ratio by the use Rhodocoat water base isocyanic ester of X EZ-D401 (from Rhodia).These results have been summed up in table 9～11.
Embodiment 7: UV-cured resin
Hyperbranched resin according to the method for preparing ultraviolet light polymerization.The composition and the character of used resin provide in table 12, by the HBNP of these resins form and character provides in table 13.
Embodiment 8: the preparation of ultraviolet-curing paint
The HBNP preparation of the uv-curable of ultraviolet-curing paint from table 13.The prescription of coating provides in table 14.This coating adds the IV preparation then by mixing I～III.After 5 minutes, add V, add VI then, remix 5 minutes.Add composition VII, VIII, IX and X successively.Mixture was stirred 5 minutes.Lamp with a 120w/in makes the HBNP institute coatings formulated of example A-1 solidify with 10 meters/minute speed.The Konig hardness of coating is 94, is 92 60 ° glossiness, and snappiness is 4%.
Table 14
It should be understood that the present invention can not be limited in this paper illustrated and the concrete prescription of description and the arrangement of umber, and be included in all modification within the claim scope.
Claims (27)
1. form the method for highly-branched polymers, described method comprises:
Make the sour functionality acrylic resin or the styrene-propene acid that are scattered in the water be resin and have many epoxy functional resin reaction of at least two epoxide groups to prepare first highly-branched polymers; And
Make described first highly-branched polymers and monocycle oxygen functionality resin reaction to form the aqueous dispersion of the second highly branched and further functionalized polymkeric substance subsequently.
2. the described method of claim 1, wherein said sour functionality acrylic resin or styrene-propene acid are that resin is that acrylic resin, metha crylic resin, the styrene-propene acid of sour functionality is resin or vinylbenzene-metha crylic resin.
3. the described method of claim 1, wherein said first highly-branched polymers is a microgel.
4. the described method of claim 1, wherein said second highly-branched polymers is a microgel.
5. the described method of claim 1, wherein said sour functionality acrylic resin or styrene-propene acid are that resin also contains hydroxy functional group.
6. the described method of claim 1, the weight percent of wherein said second highly-branched polymers in described aqueous dispersion is at least 40 weight %.
7. the described method of claim 2, wherein said sour functionality acrylic resin or styrene-propene acid are the number-average molecular weight (M of resin
n) be about 1000～10000, acid number is about 25～300, hydroxyl value is about 1～250.
8. the described method of claim 2, wherein said sour functionality acrylic resin or styrene-propene acid are that resin is to be selected from following monomer prepared sour functionality acrylic resin or metha crylic resin by one or more: vinylformic acid 2-hydroxyl ethyl ester, methacrylic acid 2-hydroxyl ethyl ester, vinylformic acid 2,3-hydroxypropyl acrylate, methacrylic acid 2,3-hydroxypropyl acrylate, vinylformic acid 2,4-hydroxy butyl ester and methacrylic acid 2, the 4-hydroxy butyl ester.
9. the described method of claim 1, the wherein said many epoxy functional resin that contains at least two epoxide groups is diepoxy resin, many epoxy functional resin or its mixture.
10. the described method of claim 9, the oxirane value of wherein said many epoxy functional resin is about 100～1000.
11. the described method of claim 1, the wherein said many epoxy functional resin that contains at least two epoxide groups is 2-glycidyl ether resin, cyclohexanedimethanodiglycidyl diglycidyl ether resin, poly(propylene oxide) 2-glycidyl ether resin or bisphenol A diglycidyl ether resin, or their any two or more mixture or adulterants.
12. the described method of claim 1, wherein said monocycle oxygen functionality resin are simple function.
13. the described method of claim 1, wherein said monocycle oxygen functionality resin also are hydroxyl functional.
14. the described method of claim 1, wherein said monocycle oxygen functionality resin is glycidyl ether resin, glycidyl ester resin or its mixture.
15. the described method of claim 1, the glycidyl ester that wherein said monocycle oxygen functionality resin is glycidyl methacrylate, neodecanoic acid, dihydroxyphenyl propane monoglycidyl ether, 2-ethylhexyl glycidyl ether or they are the mixture of two or more arbitrarily.
16. the described method of claim 2, wherein said sour functionality acrylic resin or styrene-propene acid are that resin is to be selected from the prepared sour functionality acrylic resin of following monomer from one or more, metha crylic resin: vinylformic acid 2-hydroxyl ethyl ester, methacrylic acid 2-hydroxyl ethyl ester, vinylformic acid 2, the 3-hydroxypropyl acrylate, methacrylic acid 2, the 3-hydroxypropyl acrylate, vinylformic acid 2, the 4-hydroxy butyl ester, methacrylic acid 2, the 4-hydroxy butyl ester, methyl acrylate, ethyl propenoate, the vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, the vinylformic acid n-pentyl ester, the vinylformic acid isopentyl ester, isobornyl acrylate, the just own ester of vinylformic acid, vinylformic acid 2-ethyl butyl ester, 2-EHA, the vinylformic acid n-octyl, vinylformic acid ester in the positive last of the ten Heavenly stems, vinylformic acid methyl cyclohexane ester, vinylformic acid ring pentyl ester, cyclohexyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, methacrylic acid 2-hydroxyl ethyl ester, n propyl methacrylate, n-BMA, isopropyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, the methacrylic acid n-pentyl ester, the just own ester of methacrylic acid, the methacrylic isoamyl valerate, the secondary butyl ester of methacrylic acid, the methacrylic tert-butyl acrylate, methacrylic acid 2-ethyl butyl ester, methyl methacrylate base cyclohexyl, the methacrylic acid cinnamic ester, methacrylic acid crotons ester, cyclohexyl methacrylate, methacrylic acid ring pentyl ester, methacrylic acid 2-ethoxy ethyl ester or isobornyl methacrylate.
17. the described method of claim 1, the M of the wherein said second highly branched and further functionalized polymkeric substance
nFor about 2500 to up to gelation point, acid number is about 15～250, and hydroxyl value is about 10～260.
18. by the formed highly-branched polymers of the method for claim 1.
19. the described highly-branched polymers of claim 18, wherein said highly-branched polymers is a microgel.
20. printing-ink, it comprises by the formed highly-branched polymers of the method for claim 1.
21. the described printing-ink of claim 20, wherein said sour functionality acrylic resin or styrene-propene acid are resin is that acrylic resin, metha crylic resin, the styrene-propene acid of sour functionality is resin or vinylbenzene-metha crylic resin.
22. the described printing-ink of claim 20, wherein said first highly-branched polymers is a microgel.
23. the described printing-ink of claim 20, wherein said second highly-branched polymers is a microgel.
24. ultraviolet-curing paint, it comprises by the prepared highly-branched polymers of the method for claim 1.
25. the described ultraviolet-curing paint of claim 24, wherein said sour functionality acrylic resin or styrene-propene acid are resin is that acrylic resin, metha crylic resin, the styrene-propene acid of sour functionality is resin or vinylbenzene-metha crylic resin.
26. the described ultraviolet-curing paint of claim 24, wherein said first highly-branched polymers is a microgel.
27. the described ultraviolet-curing paint of claim 24, wherein said second highly-branched polymers is a microgel.
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| US95268907P | 2007-07-30 | 2007-07-30 | |
| US60/952,689 | 2007-07-30 | ||
| PCT/US2008/071454 WO2009018264A2 (en) | 2007-07-30 | 2008-07-29 | Water-based dispersions of highly-branched polymers |
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| CN101842417B CN101842417B (en) | 2013-07-31 |
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|---|---|
| US (2) | US7887626B2 (en) |
| EP (2) | EP2173791B1 (en) |
| JP (1) | JP5389803B2 (en) |
| KR (1) | KR101543813B1 (en) |
| CN (1) | CN101842417B (en) |
| AU (1) | AU2008282279B2 (en) |
| CA (1) | CA2694758C (en) |
| ES (2) | ES2486297T3 (en) |
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-
2008
- 2008-07-29 CN CN200880108931.6A patent/CN101842417B/en active Active
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| CA2694758C (en) | 2015-05-05 |
| CN101842417B (en) | 2013-07-31 |
| JP2010535280A (en) | 2010-11-18 |
| EP2173791B1 (en) | 2014-06-18 |
| US20090036570A1 (en) | 2009-02-05 |
| ES2486297T3 (en) | 2014-08-18 |
| EP2778192B1 (en) | 2015-12-23 |
| EP2173791A4 (en) | 2011-04-27 |
| US7887626B2 (en) | 2011-02-15 |
| EP2778192A1 (en) | 2014-09-17 |
| AU2008282279B2 (en) | 2013-04-04 |
| CA2694758A1 (en) | 2009-02-05 |
| WO2009018264A2 (en) | 2009-02-05 |
| AU2008282279A1 (en) | 2009-02-05 |
| ES2562036T3 (en) | 2016-03-02 |
| USRE44931E1 (en) | 2014-06-03 |
| JP5389803B2 (en) | 2014-01-15 |
| MX2010001083A (en) | 2010-03-24 |
| MX344150B (en) | 2016-12-07 |
| KR101543813B1 (en) | 2015-08-11 |
| WO2009018264A3 (en) | 2009-05-22 |
| EP2173791A2 (en) | 2010-04-14 |
| KR20100056469A (en) | 2010-05-27 |
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